Polythiazoles and method of preparation from diphenols and dihalide dibenzothiazolic compounds

ABSTRACT

NEW POLYCONDENSATES RESULTING FROM THE CONDENSATION OF DIBENZOTHIAZOLIC DIHALOGENATED DERIVATIVE A WITH BIPHENOLS B WITH THE GENERAL FORMULA   -((BENZOTHIAZOL-2,5-YLENE)-J-(BENZOTHIAZOL-5,2-YLENE)-O-   (1,4-PHENYLENE)-J&#39;&#39;-(1,4-PHENYLENE)-O)N-((BENZOTHIAZOL-2,6-   YLENE)-J-(BENZOTHIAZOL-6,2-YLENE)-O-(1,4-PHENYLENE)-J&#39;&#39;-   (1,4-PHENYLENE)-O)N-   WHERE J AND 4&#39;&#39; JUNCTIONS WHICH MAY BE SELECTED FROM THE FOLLOWING LIST:   A SIMPLE COVALENT BOND; A BIVALENT ATOM SUCH AS -O-,-S-,-SE-; A BIVALENT GROUP SUCH AS   -CO-, -C(=S)-, -SO2, -CO-NH-, -C(=S)-NH-, -NH-CO-NH,   -NH-C(=S)-NH-, -N=N-, -CH=CH-, -CH(-OH)-, -C(-R1)(-R2)-   WHERE R1 AND R2 ARE HYDROGEN ATOMS OR ALIPHATIC, ALICYCLIC OR AROMATIC RADICALS. A PROCESS FOR SYNTHESIZING THESE POLYCONDENSATES, CONSISTING OF HEATING AN EQUIMOLECULAR MIXTURE OF A AND B, DISSOLVED IN AN ANHYDROUSS INVERT SOLVENT, TO BETWEEN 130 AND 180*C., IN THE PRESENCE OF AN EXCESS OF ACID ACCEPTOR, UNDER STRICTLY ANHYDROUS CONDITIONS AND IN A NITROGEN ATMOSPHERE FOR 100 TO 150 HOURS, WHILE BEING STIRRED VIGOROUSLY. THE APPLICATION OF THESE POLYCONDENSATES TO THE PREPARATION OF FILMS AND WARNISHES.

United States Patent 3,761,447 POLYTHIAZOLES AND METHOD OF PREPARA- TIONFROM DIPHENOLS AND DIHALIDE DI- BENZOTHIAZOLIC COMPOUNDS ChristianBlaise, Jarville, Pierre Lochon, Nancy, and Jean Neel, Villers lesNancy, France, assignors to Societe Anonyme dite: Aquitaine TotalOrganico, Courbevoie, France No Drawing. Filed Aug. 4, 1971, Ser. No.169,136 Claims priority, applicgtziggll rance, Aug. 7, 1970, 7 3

Int. Cl. C08g 33/02 US. Cl. 260-49 10 Claims ABSTRACT OF THE DISCLOSURENew polycondensates resulting from the condensation of dibenzothiazolicdihalogenated derivative A with biphenols B with the general formula3,761,447 Patented Sept. 25, 1973 "ice These polymers are obtained fromhalogenated derivatives of dibenzothiazolic compounds A With thefollowing general Formulae, I and II:

Dibenzothiazolic derivative with 5,5 junction Dibenzothiazolicderivative with 6,6 junction (ll-O C-Ol where J and I are junctionswhich may be selected from the following list:

a simple covalent bond; a bivalent atom such as -O-, S-, -Se-; abivalent group such as where R and R are hydrogen atoms or aliphatic,alicyclic or aromatic radicals.

A process for synthesizing these polycondensates, consisting of heatingan equimolecular mixture of A and B, dissolved in an anhydrous, inertsolvent, to between and 180 C., in the presence of an excess of acidacceptor, under strictly anhydrous conditions and in a nitrogenatmosphere for 100 to hours, while being stirred vigorously.

The application of these polycondensates to the preparation of films andvarnishes.

The invention concerns the synthesis of new heat-stable polycondensates,endowed with sufficient mechanical tenacity and solubility to enablethem to be used as films, or in the composition of varnishes.

such as biphenols, diamines, bimercaptans and bithiophenols.

In the case of biphenols with Formula IH below, polymers of high thermalstability are obtained, with suificient mechanical tenacity andsolubility to enable them to be used as films, or in the composition ofvarnishes.

III

The bivalent junction J is selected from the same list as J.

The polycondensates obtained in accordance with the present inventionhave the following general formulae:

C/N\ J\ N\CO- J' 0 s@ @l 111 Formula I (I: SO

5,5'-bi-(2-chloro benzothiazolyl) sulphone, melting point afterrecrystallization in cyclohexanone and chloroform 262 C.;

Formula II (J =covalent bond) 6,6'-bi-(2-chloro benzothiazolyl), meltingpoint after recrystallization in cyclohexanone, chloroform or dioxan 2320.;

Formula II (I: SO;,))

6,6'-bi-(2-chloro benzothiazolyl) sulphone, melting point afterrecrystallization in white spirit and benzene 258 C.;

Formula II (I: O)

melting point after recrystallization in heptane or a wateralcoholmixture 109 C.

Derivatives B with Formula 111 include the following examples:

Formula III (J '=covalent bond) 4,4'-dihydroxy biphenyl, melting pointafter recrystallization in a /100 water-alcohol mixture 275 C.;

Formula III J= C- CHI 4,4-dihydroxy 2,2-diphenyl propane, melting pointafter recrystallization in toluene 158 0.;

Formula III (J -SO 4,4'-dihydroxy diphenylsulphone, melting point afterrecrystallization in water 248 C.

The reaction solvent must also be strictly anhydrous. This result can beobtained by subjecting it to azeotropic distillation after addingbenzene or toluene, or by contact with an energetic drying agent.Solvents with a high boiling point are generally used, belonging eitherto the category of hydrocarbons (dekaline, tetraline, o-xylene,pseudocumene, mesitylene), or that of aprotic liquids(dimethylsulphoxide, o-dimethoxybenzene, anisol, diglime, triglime,tetramethylene sulphone, hexamethylphosphorotriamide).

The acid acceptor added to facilitate the reaction may be a tertiaryorganic amine of low volatility, but it is better to use an oxide oranhydrous basic inorganic salt such as an alkaline or alkaline-earthcarbonate or metaborate, in powder form.

Polycondensation is performed as follows.

2.5 m./moles of the reagent B, 2.5 m./moles of the dichlorinated reagentA (I or II), and 150 ml. of solvent are placed in turn in a 250 ml.reactor equipped with a mechanical stirring device, surmounted by acooler protected from atmospheric humidity by a tube containing a dryingagent, and inside which a flow of nitrogen is maintained.

The appliance is heated to 100 C. for sufficient time to allow themixture to become homogeneous. The acid acceptor is then added, inconsiderable excess in relation to the amount needed to neutralize theacid produced by the reaction. Two to five times the theoreticalquantity is normally used.

The mixture, stirred vigorously, is then heated to above C. for between100 and hours. The polycondensate forms gradually, and begins toprecipitate after about 48 hours. At the end of the operation, the solidis isolated, extracted with boiling water and washed with acetone oralcohol. This produces a white polymer, which is vacuum-dried at 150 C.

The following examples, given to illustrate the present invention,contain some additional explanation, referring to each individual case.Among these details, inherent viscosities m are expressed in m1. gf andcorrespond to measurements taken at 25 C., using solutions obtained bydissolving 500 mg. of the polymer being examined in 100 ml. ofdichloracetic acid. The thermal stability of the differentpolycondensates was assessed by differential thermal analysis, operatingin the presence of air, using the apparatus, type M constructed by theFrench National Scientific Research Centre, the Centre National de laRecherche Scientifique, set so as to ensure a temperature rise of 100 C.an hour. The recording obtained is characterized by two temperaturesselected in the part of the line describing the thermal degradation ofthe sample. The first is defined by the intersection of the axis of theabscissae and the tangent taken to the point of infiexion situated inthe upward part of the outline, and the second corresponds to themaximum point on the curve. These two temperatures indicate the lowerand upper limits, respectively, of what is referred to as the thermaldecomposition zone.

These details are shown in Table 1, which also gives the applications ofthe products examined, which may be used in the form of films, or in thecomposition of varnishes. These films, which are usually obtained byallowing a collodion, produced by dissolving the polymer indichloracetic acid, to evaporate, are transparent and colourless.

Generally, such polycondensates are of high thermal stability,decomposing in air only above 400 C. They dissolve only in a smallnumber of very active solvents, such as dichloracetic acid and certainphenols. Finally, they have extremely useful mechanical tenacity whenused in the form of film or varnish.

The invention is illustrated by the following examples.

EXAMPLE 1 Polycondensation of 6,6-bi-(2-chloro benzothiazolyl) sulphone(Formula II, where I: -SO;) with 4,4'-dihydroxy diphenylsulphone(Formula III, where J SO 1002 mg. of 6,6'-bi-(2-chloro benzothiazolyl)sulphone and 625 mg. of 4,4'-dihydroxy diphenylsulphone arepolycondensed, at 145 C., in o-dimethoxybenzene, in the presence ofpowdered anhydrous sodium carbonate (2 /2 times the amount theoreticallyneeded to neutralize the hydrochloric acid produced), and produce 1100mg. (73 yield) of the required polycondensate, in the form of a white,film-forming polymer with an inherent viscosity of 77 ml. grand thethermal decomposition zone of which lies between 420 and 530 C.

EXAMPLE 2 Polycondensation of 6,6-bi-(2-chloro benzothiazolyl) sulphone(Formula II, where J -SO with 4,4'-dihydroxy 2,2-diphenyl propane(Formula 11 1, where 1:

1002 mg. of 6,6'-bi-(2-chloro benzothiazolyl) sulphone and 570 mg. of4,4'-dlhydroxy 2,2-dipheny1 propane are polycondensed at C. inpseudocum-ene, in the presence of anhydrous sodium carbonate (twice theamount theoretically needed), and produce 1200 mg. (85% yield) of thedesired polycondensate, in the form of a white filmforming polymer withan inherent viscosity of 95 ml. g.-

and the thermal decomposition zone of which lies between 395 and 460 C.

EXAMPLE 3 Polycondensation of 6,-6-bi-(2-chloro benzothiazolyl) sulphone(Formula II, where J: -SO with 4,4'-dihydroxy biphenyl (Formula III,where I is a simple covalent bond).

1002 mg. of 6,6-bi-(2-chloro benzothiazolyl) sulphone and 465 mg. of4,4'-dihydroxy biphenyl are polycondensed at 145 C. ino-dimethoxybenzene, in the presence of anhydrous sodium carbonate (fourtimes the theoretical amount needed), producing 940 mg. (73% yield) ofthe desired polycondensate. It is a film-forming polymer with aninherent viscosity of 68 ml. g." and the thermal decomposition zone ofwhich lies between 430 and 527 C.

EXAMPLE 4 Polycondensation of 5,5-bi-(2-chloro benzothiazolyl) sulphone(Formula I, where J: --SO with 4,4'-dihydroxy biphenyl (Formula III,where I is a simple covalent bond).

1002. mg. of 5,5'-bi-(2-chloro benzothiazolyl) sulphone and 465 mg. of4,4'-dihydroxy biphenyl are polycondensed at 160 C. ino-dimethoxybenzene, in the presence of anhydrous sodium carbonate (fourtimes the theoretical amount needed), producing 900 mg. (71% yield) ofthe desired polycondensate. It is a polymer, solutions of which havevarnish properties. The inherent viscosity is 31 ml.

polymer deposit a varnish after evaporation. The inherent viscosity isml. gf and its thermal decomposition zone lies between 440 and 530 C.

EXAMPLE 6 EXAMPLE 7 Preparation of 6,6-bi-(2-N-piperidinobenzothiazolyl) sulphone.

This example illustrates the reactivity, with regard to amines, of thetwo chlorine atoms in 6,6-bi-(2-chlorobenzothiazolyl) sulphone.

2 g. (0.005 mole) of 6,6'-bi-(2-chloro benzothiazolyl) sulphone aredissolved in ml. of tetrahydrofuran heated to boiling point, and 850 mg.(0.01 mole) of anhydrous piperidin are added. After two hours reflux, itis allowed to cool, and the resulting product, which has precipitated,

gr and its thermal degradation zone lies between 470 30 is isolated. Theproduct is a white solid, which melts at and 558 C.

272 C. The operation gives 100% yield.

TABLE I Reaction conditions Properties of polycondensate Nature ofpolycondensate Zone of Percent Temp. Yield ninh degradation Applica- J ISolvent COaNa2 a 0.) (percent) (ml.g.- 0.) tion -SO (6,6) -SO2o-Dimethoxybenzene.--..- 250 145 73 77 420-530 Film.

SO (6,6') CH3 Pseudocumene 200 155 85 95 395-460 Do.

S02- (6,6') Covalent bond o-Dimethoxybenzene 400 145 33 68 430-527 Do. 0do do 400 160 71 31 470-558 Varnish. SOz- (5,5) -S02- do 00 160 30440-530 Do. Covalent bond (6-6) Convalent bond do 400 15 42 456-508Film.

Characteristics of the polycondensates described in examples:

a Quantity of anhydrous sodium carbonate added, expressed as a percentof the amount theoretically needed to neutralize the hydrochloric acidproduced.

EXAMPLE 5 Polycondensation of 5,5-bi-(2-chloro benzothiazolyl) sulphone(Formula I, where J: SO with 4,4'-di I o-o-- .T 0 @L/ b Inherentviscosity measured in a solution in dichloracetic acid and containing0.5 g. polymer in ml. solvent.

v Heat decomposition zone defined as indicated in the text.

What is claimed is:

1. A member selected from the group consisting of film formingpolycondensates consisting essentially of repeating units of theformulae:

wherein J is a member selected from the group consisting of S0 and acovalent bond and J' is a member selected from a group consisting of S0a covalent bond, and

2. A polycondensate according to claim 1 consisting essentially ofrepeating units of the following structural formula:

3. A polycondensate according to claim 1 consisting essentially ofrepeating units of the following structural formula:

E 01 I \N N/ a J 4. A polycondensate according to claim 1 consistingessentially of repeating units of the following structural formula:

I so a ne 5. A polycondensate according to claim 1 consistingessentially of repeating units of the following structural formula:

6. A polycondensate according to claim 1 consisting essentially ofrepeating units of the following structural formula:

7. A polycondensate according to claim 1 consisting essentially ofrepeating units of the following structural formula:

I S --o 8. A process for the production of the polycondensate accordingto claim 1 comprising reacting a compound selected from the groupconsisting of dibenzothiazolic derivatives having a 5,5 junction of theformula wherein I is a member selected from the group consisting of S0and a covalent bond-and a dibenzothiazolic derivative with a 6,6junction of the formula wherein J is as defined above-with a compound ofthe formula wherein J is a member selected from the group consisting ofS0 a covalent bond and 9 10 10. A process according to claim 8 whereinsaid acid 3,397,187 8/1968 Mecum 26079 acceptor is a member selectedfrom the group consisting 3,424,720 1/1969 Rudner et al. 26047 oftertiary amines with low volatility, alkaline-earth oxides andalkaline-earth salts. WILLIAM H. SHORT, Primary Examiner 5 I ReferencesCited L L LEE, Assistant Examiner UNITED STATES PATENTS US. Cl. X.R.

3,267,081 8/1966 Rudner et a1. 260-78.4 117161 UN; 26031.2 N, 33.4 P,61, 79 R

